WO2007055323A1 - Dispositif d’affichage, event a anneau de verre, anneau de verre de phosphate, et procede de production correspondant - Google Patents

Dispositif d’affichage, event a anneau de verre, anneau de verre de phosphate, et procede de production correspondant Download PDF

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Publication number
WO2007055323A1
WO2007055323A1 PCT/JP2006/322473 JP2006322473W WO2007055323A1 WO 2007055323 A1 WO2007055323 A1 WO 2007055323A1 JP 2006322473 W JP2006322473 W JP 2006322473W WO 2007055323 A1 WO2007055323 A1 WO 2007055323A1
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WO
WIPO (PCT)
Prior art keywords
glass ring
phosphate glass
tube
glass
display device
Prior art date
Application number
PCT/JP2006/322473
Other languages
English (en)
Japanese (ja)
Inventor
Yoshiaki Kai
Shinya Hasegawa
Original Assignee
Matsushita Electric Industrial Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Matsushita Electric Industrial Co., Ltd. filed Critical Matsushita Electric Industrial Co., Ltd.
Priority to US12/092,768 priority Critical patent/US20100006313A1/en
Priority to JP2007544197A priority patent/JP4124804B2/ja
Publication of WO2007055323A1 publication Critical patent/WO2007055323A1/fr
Priority to US12/495,257 priority patent/US7737619B2/en

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J11/00—Gas-filled discharge tubes with alternating current induction of the discharge, e.g. alternating current plasma display panels [AC-PDP]; Gas-filled discharge tubes without any main electrode inside the vessel; Gas-filled discharge tubes with at least one main electrode outside the vessel
    • H01J11/20—Constructional details
    • H01J11/54—Means for exhausting the gas
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/38—Exhausting, degassing, filling, or cleaning vessels
    • H01J9/385—Exhausting vessels
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/08—Frit compositions, i.e. in a powdered or comminuted form containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/16—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions with vehicle or suspending agents, e.g. slip
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J11/00—Gas-filled discharge tubes with alternating current induction of the discharge, e.g. alternating current plasma display panels [AC-PDP]; Gas-filled discharge tubes without any main electrode inside the vessel; Gas-filled discharge tubes with at least one main electrode outside the vessel
    • H01J11/10—AC-PDPs with at least one main electrode being out of contact with the plasma
    • H01J11/12—AC-PDPs with at least one main electrode being out of contact with the plasma with main electrodes provided on both sides of the discharge space
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J11/00—Gas-filled discharge tubes with alternating current induction of the discharge, e.g. alternating current plasma display panels [AC-PDP]; Gas-filled discharge tubes without any main electrode inside the vessel; Gas-filled discharge tubes with at least one main electrode outside the vessel
    • H01J11/20—Constructional details
    • H01J11/48—Sealing, e.g. seals specially adapted for leading-in conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J7/00—Details not provided for in the preceding groups and common to two or more basic types of discharge tubes or lamps
    • H01J7/14—Means for obtaining or maintaining the desired pressure within the vessel
    • H01J7/22—Tubulations therefor, e.g. for exhausting; Closures therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/24—Manufacture or joining of vessels, leading-in conductors or bases
    • H01J9/26—Sealing together parts of vessels
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/24—Manufacture or joining of vessels, leading-in conductors or bases
    • H01J9/26—Sealing together parts of vessels
    • H01J9/261—Sealing together parts of vessels the vessel being for a flat panel display
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/131—Glass, ceramic, or sintered, fused, fired, or calcined metal oxide or metal carbide containing [e.g., porcelain, brick, cement, etc.]
    • Y10T428/1317—Multilayer [continuous layer]

Definitions

  • the present invention relates to a display device such as a plasma display panel or a field emission display, and more particularly to a display device having excellent airtightness in a light emission excitation source space.
  • the present invention also relates to a vent pipe with a glass ring and a phosphate glass ring suitable for manufacturing such a display device.
  • Display devices such as plasma display panels (hereinafter referred to as PDPs) and field emission displays (hereinafter referred to as FEDs) are attracting attention as thin display devices that can achieve both large screens and thin and light weights. It has been.
  • PDPs plasma display panels
  • FEDs field emission displays
  • a light emission excitation source space is formed between a pair of panels.
  • This emission excitation source space is, for example, a discharge space filled with a discharge gas mainly composed of a rare gas in the case of a PDP, or a vacuum space in which an electron beam emitted from an electron source can be extracted without being attenuated in the case of an FED, for example. It is a space equivalent to, and high airtightness is required.
  • vent pipe When manufacturing a display device, it is necessary to adjust the atmosphere in the emission excitation source space.
  • the atmosphere is adjusted through a pipe (vent pipe) attached so as to communicate with a hole (vent hole) formed in the panel.
  • the vent pipe has a pipe having a tip shape having excellent stability, for example, a diameter-expanded portion 53 and a flange portion 52 as shown as a pipe 12 in FIG. 7A.
  • Tube is used.
  • the glass ring After aligning the vent holes, vent pipe and glass ring through-holes, the glass ring is melted to form a glass member, so that the pipe 12 becomes the hole formed in the panel lb as shown in Figure 7B. 11 on the panel lb through the glass member 23 so as to cover Attached.
  • the water resistance of the glass ring is significantly reduced.
  • the reason for the high deliquescence of oxyphosphorus is that the phosphorus atom is pentavalent but is 4-coordinated to the oxygen atom, so phosphorus oxide is unstable with three shared oxygens.
  • An object of the present invention is to improve the long-term moisture resistance performance of a display device while using phosphoric acid-based glass as a material for a glass ring (glass member) for attaching a vent pipe on a panel. Furthermore, an object of the present invention is to provide an air pipe with a glass ring, a phosphate glass ring, and a method for manufacturing the same, suitable for manufacturing the display device.
  • the present invention provides a display device including a panel in which holes are formed, a phosphate glass member, and a tube that is attached to the panel via the phosphate glass member and covers the holes.
  • the phosphate glass member is joined along at least a part of the inner wall surface of the tube and a part of the panel, and the entire circumference of the end surface of the tube on the hole side is the vice.
  • Another aspect of the present invention is a vent pipe with a glass ring for manufacturing the above display device, which is joined along at least a part of the inner wall surface of the vent pipe.
  • a phosphate glass ring for manufacturing the display device, wherein the shape is in contact with at least a part of an inner wall surface of a tube attached on the panel.
  • the inclination of the outer peripheral surface with respect to a plane perpendicular to the rotation axis of the rotating body is 0
  • a phosphate glass ring that is in the range of greater than 90 degrees and less than 90 degrees and substantially free of binder.
  • Another aspect of the present invention is a method for producing a phosphate glass ring as described above, wherein the phosphate glass ring is solid in a 25 ° C atmosphere and has a boiling point of 400 ° C.
  • a step of forming a frit binder mixture comprising the following binder, and obtaining a molded ring having a surface corresponding to the outer peripheral surface of a predetermined rotating body and having an end surface with a through-hole opened; And a binder removal step of removing the binder by heating the molded body ring.
  • the phrase "substantially” does not contain a binder means that the content of a known organic substance used as a glass binder is in the range of less than lppm, more specifically less than lppb. . “Ppm” means mass parts per million and “ppb” means mass parts per billion.
  • the content of organic substances can be evaluated using a known method such as gas chromatography mass spectrometry (GC-MS).
  • the present invention while using phosphate glass as a material of a glass ring (glass member) involved in mounting a tube on a panel, contact of moisture in the outside air with the glass member is blocked.
  • the long-term moisture resistance performance of the display device can be improved.
  • FIG. 1 is a cross-sectional view of an example of a display device of the present invention.
  • FIG. 2 is an exploded perspective view of an example of the display device of the present invention.
  • FIG. 3A is a diagram for explaining an example of a method for manufacturing a display device of the present invention.
  • FIG. 3B is a diagram for explaining an example of the display device manufacturing method of the present invention.
  • FIG. 4A is a cross-sectional view of an example of a phosphoric acid-based glass ring and a vent pipe having the glass ring incorporated therein, which are used for manufacturing the display device of the present invention.
  • FIG. 4B is a diagram for explaining an example of a state where a tube is attached on a panel via a phosphate glass member in the display device of the present invention.
  • FIG. 5A is a cross-sectional view of another example of a phosphoric acid-based glass ring and a vent pipe incorporating the glass ring, which are used for manufacturing the display device of the present invention.
  • FIG. 5B is a diagram for explaining another example of a state in which a tube is attached on a panel via a phosphate glass member in the display device of the present invention.
  • FIG. 6A is a cross-sectional view of another example of a phosphoric acid-based glass ring and a vent pipe having the glass ring incorporated therein, which are used for manufacturing the display device of the present invention.
  • FIG. 6B is a plan view of the display device of the present invention through the phosphate glass member It is a figure for demonstrating another example of the state in which the pipe was attached on the panel.
  • FIG. 7A is a cross-sectional view for explaining the structure of a glass ring of a comparative example and a conventional example.
  • FIG. 7B is a diagram for explaining a state in which the tube is attached on the panel via the glass member in the display devices of the comparative example and the conventional example.
  • FIG. 8 is a cross-sectional view of another example of a vent pipe incorporating a glass ring used for manufacturing a display device of the present invention.
  • the light emission excitation source space in the display device is adjusted after the internal atmosphere is adjusted via a vent pipe attached on the panel so as to cover the vent hole formed in the panel during manufacture. Airtight by sealing the opposite end.
  • a vent pipe attached on the panel so as to cover the vent hole formed in the panel during manufacture. Airtight by sealing the opposite end.
  • the tube has a shape capable of enhancing the bonding stability between the tube and the panel, that is, a shape in which stress applied to a contact portion between the tube and the panel is easily dispersed.
  • it has a pipe part and a flange part connected to the pipe part, and the flange part forms an end face on the hole side in the pipe.
  • the narrow pipe part has a diameter larger than the narrow pipe part and A structure having an enlarged diameter portion arranged on the panel side with respect to the thin tube portion, and a structure having an enlarged diameter portion that does not substantially have the thin tube portion and increases in diameter as it approaches the panel. It is By forming an enlarged diameter portion or flange portion at the tip of the tube, the tip diameter of the tube can be increased, and joint stability when the tube is held perpendicular to the panel is increased.
  • Examples of the shape of the enlarged diameter portion include (1) a shape in which the inner and outer diameters are constant in the extending direction of the tube (for example, a cylindrical shape as shown as the tube 16 in FIG. 5A), and (2) the first The shape including the inner and outer diameters of the second and the second inner and outer diameters different from the first inner and outer diameters, more specifically, (2A) increases as it approaches the end face, and its enlargement ratio increases to a constant or approaches the end face Shape (for example, flare shape as shown as tube 12 in Fig.
  • a tube having a diameter-enlarged portion corresponding to the above (1), (2A) and (2B) is referred to as a tube with a cylindrical portion and a flare, respectively. It is called a tube with a part and a bell part.
  • the material of the tube is not particularly limited, but glass is preferably used as the material from the viewpoint of smooth mounting on the panel.
  • the tube is arranged so that the entire circumference of the end surface on the hole side is in contact with the panel so as to cover the hole formed in the panel.
  • the fact that the entire circumference of the end face is in contact with the panel is the extent that the phosphate glass member placed in the tube can be blocked from contact with moisture in the outside air and the deterioration of the glass member due to moisture in the outside air can be prevented.
  • the end face and the panel are brought close to each other, and the purpose is to eliminate the state where there is an interval of less than 5 ⁇ m between the end face and the panel as shown in the examples described later. is not.
  • the phosphate glass member is bonded along at least a part of the inner wall surface of the tube and a part of the panel as described above. As described above, the phosphate glass member is not exposed to the outside air because the entire circumference of the end face of the tube is in contact with the panel. When the phosphate glass member is not exposed to the outside air, the phosphate glass member in the tube is not allowed to pass through a gap of less than 5 m that is allowed to exist between the end surface of the tube and the panel. It is not intended to exclude the state exposed to the outside air.
  • the phosphoric acid-based glass member is preferably bonded along the entire wall surface of the outer wall surface and further along the inner wall surface of the tube.
  • the phosphate glass member is preferably joined along at least a part of the inner wall surface of the enlarged diameter portion.
  • the shape of the phosphoric acid-based glass member is a shape having a surface corresponding to the outer peripheral surface of the predetermined rotating body, it is easy to realize the above-described bonding state.
  • the outer peripheral surface of a given rotating body For example, a surface shape in which the inclination of the outer peripheral surface with respect to a plane orthogonal to the rotation axis of the rotating body is in the range of greater than 0 degrees and less than 90 degrees can be exemplified.
  • the tube is a tube with a cylindrical portion, a tube with a flare portion, and a tube with a bell portion
  • the outer shape of the rotating body is preferably a columnar shape, a truncated cone shape, and a bell shape, respectively.
  • the phosphate glass member in the display device has a shape corresponding to the outer peripheral surface of the predetermined rotating body, and the inclination of the outer peripheral surface with respect to the plane orthogonal to the rotation axis of the rotating body is 0 degree. Larger than 90 degrees and may be joined to at least a part of the inner wall surface of the pipe on the outer peripheral surface.
  • the outer shape of the rotating body may be a cylindrical shape, a truncated cone shape, or a bell shape.
  • the area where the phosphate glass member is bonded to the panel is as large as possible.
  • the phosphoric acid-based glass member heats the phosphoric acid-based glass ring after the ventilation tube is disposed on the panel in a state where the phosphoric acid-based glass ring is disposed in the tube of the venting tube. After melting, it is formed from the cocoon.
  • Phosphoric glass rings include P 2 O 3 SnO, P 2 O—SnO—ZnO, P 2 O—SnO—Si
  • Shapes glass networks such as O, P O -SnO-Al O, P O—SnO—B O, etc.
  • the phosphate glass ring does not contain lead and does not substantially contain a binder.
  • the glass may be altered or cracks may occur on the panel during heating to attach a vent pipe on the panel. You may not be able to attach the tube with force
  • the phosphoric acid-based glass ring has an outer wall from the viewpoint of improving the bondability with the inner wall surface of the vent pipe. It is desirable to form such that at least a part of the surface, or the entire outer wall surface, in particular, the entire outer wall surface is in contact with the inner wall surface of the vent pipe.
  • Examples of such a shape include a shape having a surface corresponding to the outer peripheral surface of a predetermined rotating body and an end surface having a through hole opened.
  • An example of the outer peripheral surface of the predetermined rotating body is a surface shape in which the inclination of the outer peripheral surface with respect to a plane orthogonal to the rotational axis of the rotating body is in the range of more than 0 degree and less than 90 degrees as shown in FIG. 4A.
  • the outer shape of the rotating body is preferably a columnar shape, a truncated cone shape, and a bell shape, respectively.
  • the phosphoric acid glass frit described above contains 20 mol% or more of phosphorus oxide (P 2 O 3) based on oxides.
  • the upper limit of the content of 25 is preferably 50 mol%.
  • the phosphate glass frit may further contain tin oxide (SnO).
  • SnO tin oxide
  • the upper limit of the SnO content is preferably 60 mol%.
  • sublimable binder examples include one selected from camphor (boiling point 204 ° C), naphthalene (boiling point 218 ° C) and anthracene (boiling point 354 ° C).
  • the sublimable organic substance disappears completely at a pre-baking temperature not lower than the glass transition point of the phosphate glass frit and lower than the softening point, more specifically, 250 to 450 ° C., and does not remain in the glass ring.
  • Sublimable organic substances are hydrophobic (no hydrophilic group in the molecule) and have a strong binding force, so they are effective as noinders that can form glass rings from various low-melting glass frit. .
  • the above binder typified by camphor can be almost completely removed by pre-baking (binder removal step) due to its sublimation property. Therefore, as described above, a glass ring having no residual binder can be formed. It is easy to form. In order to form a glass ring, it is possible to use the above-mentioned binders represented by camphor as phosphorous oxide (PO) as a glass material.
  • phosphorous oxide PO
  • SnO-containing glass is a residual binder with relatively low strength
  • the negative effects of one are particularly serious.
  • the more complicated the ring shape the more uniform the stress lance, and the higher the rate of defects due to glass alteration and residual binder.
  • the glass may change in quality or cracks may occur during the tube mounting operation on the panel, so that the tube can be firmly mounted on the panel. There may not be.
  • Glass containing phosphorus oxide is low in water resistance and easily deteriorates, but the organic binders such as camphor have so-called sublimation properties, so they volatilize violently in the ring creation process other than the binder removal process. Generates an airflow away from the body ring. As a result, moisture access to the molded body ring is obstructed, and during the formation of the glass ring, the phosphate glass having poor water resistance can be protected against moisture and its alteration can be prevented. For this reason, it becomes easy to form a phosphate glass ring having a complicated outer wall shape in a wrinkled state with few defects such as cracks and chips.
  • a glass ring is formed using a non-sublimating binder, for example, a high molecular binder such as polyethylene carbonate, a polyethylene glycol derivative, or polymethylstyrene disclosed in JP-A-2004-182584
  • a non-sublimating binder for example, a high molecular binder such as polyethylene carbonate, a polyethylene glycol derivative, or polymethylstyrene disclosed in JP-A-2004-182584
  • the polymer structure can be decomposed to a certain degree by heating in the binder removing step, a certain amount or more of the binder remains on the glass ring, which is difficult to remove completely.
  • the glass ring may be damaged due to residues after disassembly.
  • the content of the sublimable organic substance with respect to the phosphate glass frit is preferably in the range of 1% by mass to 20% by mass, and more preferably in the range of 5% by mass to 15% by mass.
  • the phosphate glass frit can be bound more reliably.
  • the binder content in the frit binder mixture is relative to the phosphate glass frit.
  • the content is preferably in the range of 1% by mass to 20% by mass.
  • the frit 'binder mixture is composed of, for example, 100 parts by mass of a phosphoric glass frit containing 1% by mass to 20% by mass of a sublimable organic substance, and 50 to 150 parts by mass of an organic solvent.
  • the organic solvent may be prepared by evaporating to dryness at 30 ° C or lower. The evaporation to dryness is preferably performed at a temperature as low as possible and in a short time so as not to reduce the content of the sublimable organic substance in the frit 'binder mixture.
  • the organic solvent has a boiling point of 100 ° C or lower, more preferably a boiling point of 85 ° C or lower, more specifically, ethanol, isopropanol, jetyl ether, isopropyl ether, acetone, methylethyl. It is preferable to use ketones, ethyl acetate, methylene chloride, black mouth form, 1,2-dichloroethane, etc.
  • the phosphate glass frit is in a state of further containing ZnO, SiO, Al 2 O, B 2 O, etc.
  • Phosphoric glass frit consists of Li 0, Na 0, K 0, MgO, CaO, SrO, BaO, V 2 O, Te
  • the glass composition may be in a contained state.
  • these components When these components are added, it becomes easier to control the thermal properties of the glass composition and to improve the strength.
  • the phosphate glass frit may be in a state of further containing a fire-resistant lead-free filler.
  • Lead-free fire-resistant fillers include cordierite, willemite, forsterite, annosite, dinolecon, mullite, ⁇ -eucryptite, ⁇ -spodumite, cristobalite, barium titanate, aluminum titanate, titanium oxide, tin oxide, Selected from aluminum oxide, zirconium oxide, zirconium phosphate, quartz glass, sialon, silicon nitride, silicon carbide, ⁇ -quartz solid solution, and compounds represented by the formula AD ( ⁇ )
  • ⁇ is Li, Na, K, Mg And at least one element selected from Ca, Sr, Ba, Zn, Cu, Ni and Mn, and D is at least one element selected from Zr, Ti, Sn, Nb, Al, Sc and Y. And M is at least one element selected from P, Si, W and Mo.
  • Examples of the amount of the refractory lead-free filler contained in the glass frit include a range of 0 to 70 mass%, preferably a range of 5 to 50 mass%.
  • a phosphate glass ring is obtained using the frit binder mixture described above, and a phosphate glass member is obtained by heating and melting the phosphate glass ring. For this reason, a phosphate glass ring and a phosphate glass member will be in the state which does not contain lead and an organic binder substantially. Further, the phosphate glass ring and the phosphate glass member may contain 20 mol% or more of phosphorus oxide based on the oxide. Further, the phosphate glass ring and the phosphate glass member may further contain tin oxide.
  • Examples of display devices include PDP and FED.
  • PDP and FED.
  • an example of the display device of the present invention will be described in more detail using the PDP as an example.
  • FIG. 1 is a cross-sectional view showing an example of the structure of a PDP.
  • a front panel including a substrate la (front substrate) and a back panel including a substrate lb (back substrate) are arranged to face each other, and a discharge space 2 (luminescence excitation source space) is provided therebetween. Is formed.
  • the materials of the substrates la and lb are not particularly limited, but glass is usually used.
  • a hole 11 is formed in the substrate lb, and a tube 12 is attached on the main surface of the substrate lb opposite to the discharge space 2 so as to cover the hole 11.
  • the entire end surface of the tube 12 on the hole side is in contact with the back panel. More specifically, the entire circumference of the flange portion 52 connected to the tube portion of the tube 12 is in contact with the substrate lb.
  • a phosphate glass member 13 is joined to the inside (inside the tube) of the tube 12. Phosphate glass member 13 is exposed to the outside air Not done.
  • the peripheral edges of the substrates la and lb are sealed by the peripheral sealing wall 3. Further, the end (narrow tube portion) of the tube 12 opposite to the hole side is sealed.
  • the PDP 51 has a so-called three-electrode structure. In Fig. 1, the number of partitions and data electrodes in an actual PDP are omitted.
  • FIG. 2 is a perspective view of the PDP 51 in a state where the substrate la and the substrate lb are separated.
  • illustration of the peripheral sealing wall 3 and the glass member 13 is omitted, and only a part of the substrates la and lb is shown.
  • Scan electrode 41 and sustain electrode 42 have a structure in which bus electrode (scan electrode) 41b and bus electrode (sustain electrode) 42b are laminated on transparent electrode (scan electrode) 41a and transparent electrode (sustain electrode) 42a, respectively.
  • Examples of the material of the transparent electrodes 41a and 42a include ITO (Indium Tin Oxide) and tin oxide.
  • Examples of the material of the bus electrodes 41b and 42b include aluminum, copper and silver.
  • a glass called black stripe and a black film 40 having a black pigment power are arranged to improve the black display quality and increase the contrast of the image.
  • Each electrode and the black film 40 included in the electrode group 4 can be formed on the substrate la by, for example, screen printing.
  • a dielectric layer 5 is disposed on the substrate la so as to cover the display electrode 43, and more specifically, on the dielectric layer 5 on the discharge space 2 side.
  • a protective layer 6 for protecting the dielectric layer 5 is disposed.
  • the dielectric layer 5 serves as a capacitor that accumulates charges when the PDP 51 displays an image. Examples of materials for the dielectric layer 5 and the protective layer 6 include low-melting glass and MgO, respectively.
  • a dielectric layer 8, a partition wall 9, and a stripe-shaped address electrode 7 are arranged on the substrate lb.
  • the dielectric layer 8 is arranged so as to cover the address electrode 7, and the barrier ribs 9 are parallel to each other. It is arranged to become.
  • a phosphor layer 10 is disposed between adjacent barrier ribs 9.
  • the discharge space 2 is divided into pixels by the barrier ribs 9.
  • the phosphor layer 10 includes a phosphor that emits red, green, or blue.
  • the material of the address electrode 7 and the dielectric layer 8 the same material as that of the bus electrode and the dielectric layer 5 can be used. Examples of the material for the partition wall 9 include glass and pigment.
  • the substrates la and lb are arranged so that the protective layer 6 and the barrier rib 9 face the discharge space 2, and the striped electrode group 4 and the address electrode 7 are viewed from the main surfaces of the substrates la and lb. They are placed facing each other so as to be orthogonal.
  • the discharge space 2 is filled with a discharge gas containing a rare gas such as neon or xenon.
  • the pressure of the discharge gas in the discharge space 2 can be, for example, in the range of 53329 to 79993 Pa (400 to 600 Torr).
  • the PDP 51 selectively applies a video signal voltage to the display electrode 43 to cause plasma discharge of the discharge gas, excites the phosphor contained in the phosphor layer 10 by the generated ultraviolet light, and the excited phosphor is red. Display a color image by emitting green or blue light
  • the glass member involved in mounting the tube on the panel is not exposed to the outside air. This prevents moisture in the outside air from coming into contact with the glass member and eroding the glass member, and suppresses the occurrence of slow leaks at the joint between the panel and the tube.
  • the gas pressure in the discharge space is maintained well over the long term and normal discharge is maintained.
  • the PDP 51 can be manufactured, for example, as follows.
  • Display electrodes are formed as follows on the main surface of the front substrate la, which is made of soda-lime glass having a thickness of about 2.6 mm.
  • the force shown here shows an example of forming the display electrode by a printing method. Besides this, it can be formed by a die coating method, a blade coating method, or the like.
  • a transparent electrode material ITO
  • a photosensitive paste is prepared by mixing metal (Ag) powder, organic vehicle and photosensitive resin (photodegradable resin).
  • this photosensitive paste After being applied over the pattern, it is covered with a mask having a pattern of display electrodes to be formed. Thereafter, the mask is exposed to a force, and the photosensitive paste is developed and baked (baking temperature of about 590 to 600 ° C.).
  • the nose electrodes 41b and 42b are formed on the transparent electrodes 41a and 42a.
  • the metal material of the bus electrode Pt, Au, Cu, Al, Ni, Cr, tin oxide, indium oxide, or the like may be used instead of Ag.
  • the bus electrode can be finely lined up to a line width of about 30 m, compared to the screen printing method in which the line width of 100 m is conventionally limited.
  • a known forming method in which an electrode material is formed by a vacuum deposition method, a sputtering method, or the like and then formed by etching.
  • a paste containing a lead-free dielectric glass is applied on the formed display electrode by using a screen printing method.
  • the dielectric layer 5 is formed by baking after drying for a certain period of time.
  • Lead-free dielectric glass materials include P O—SnO, P O—Sn
  • glass powders such as O—ZnO, Bi 2 O, and ZnO—B 2 O—SiO.
  • a protective layer 6 made of magnesium oxide having a thickness of about 1 ⁇ m is formed on the surface of the dielectric layer 5 by sputtering.
  • the front panel is manufactured.
  • a conductive material mainly composed of metal (Ag) is applied in stripes at regular intervals on the surface of the rear substrate lb, which has a glass soda lime strength of about 2.6 mm, by screen printing.
  • the address electrode 7 having a thickness of about 5 ⁇ m is formed.
  • a dielectric film 8 is formed by baking after drying for a certain period of time.
  • a partition wall 9 having a height of about 60 to 100 m is formed on the dielectric film 8 and between adjacent address electrodes.
  • the partition wall 9 can be formed by, for example, using a paste containing a non-lead dielectric glass used for forming the dielectric film 8, repeatedly screen-printing the paste, and firing the paste.
  • a red (R) phosphor, a green (G) phosphor, and a blue (B) phosphor is in contact with the sidewall of the partition and the dielectric film exposed between the adjacent partitions.
  • Phosphor ink containing (15 XI The 0- 3 Pa 's), using a pump, is applied by injecting between adjacent barrier ribs through a nozzle of diameter 60 m.
  • the panel is moved in the longitudinal direction of the partition wall 9 and the phosphor ink is applied in a stripe shape.
  • the phosphor layer 10 is formed by baking at around 500 ° C. for 10 minutes.
  • a knock panel can be manufactured.
  • RGB phosphors for example, the following can be used.
  • phosphor ink for example, each phosphor material 50 wt% of the volume average particle diameter of 2. 0 mu m, and E chill cellulose 1.0 mass 0/0, the solvent (alpha - Tabineoru) 49 Weight 0/0 Can be prepared by stirring and mixing with a sand mill.
  • a glass paste containing a lead-free glass frit is applied to the main surface of at least one of the front panel and the back panel so as to go around the periphery of the main surface.
  • This lead-free glass frit includes low melting point glass such as Bi-based and ZnO-B 2 O 3 -SiO.
  • Examples thereof include lath powders or mixed powders of these low-melting glass powders and fire-resistant lead-free filler powders.
  • the applied paste After the applied paste is dried for a certain period of time, it is preliminarily fired near the softening point of the lead-free glass in the glass paste, more specifically at 350 to 450 ° C, whereby a peripheral sealing member 1 Form 4.
  • the calcination time can be, for example, 30 minutes.
  • the peripheral sealing member 14 that is further baked and melted as described later is handled as the peripheral sealing wall 3 that seals between the front panel and the back panel.
  • both panels are arranged to face each other so as to be orthogonal to the electrode group 4 of the front panel and the address electrode 7 of the back panel.
  • the vent pipe represented by the flare pipe 12 shown in Fig. 4A is in contact with the pack panel so that it communicates with the vent hole 11 formed in the knock panel. Arrange as you do.
  • a glass ring represented by a frustoconical glass ring 15 shown in FIG. 4A is joined to the inner wall surface of the tube portion of the ventilation pipe.
  • the ventilation pipe may be attached to the knock panel using a phosphate glass ring and a ventilation pipe that are separated and independent from each other.
  • a ventilation tube with a glass ring disposed inside the ventilation tube with the side surface of the ring joined along at least a part of the inner wall surface of the tube portion of the ventilation tube.
  • the inside of the discharge space was evacuated to ing to a high vacuum state (about 1.0 X 10- 4 Pa), the inside is a predetermined pressure (here about 66.5 ⁇ 101kPa Until it is filled with a discharge gas such as Ne-Xe, He-Ne-Xe or He-Ne-Xe-Ar.
  • a discharge gas such as Ne-Xe, He-Ne-Xe or He-Ne-Xe-Ar.
  • the end of the air pipe opposite to the hole 11 side in other words, the end opposite to the substrate lb side (capillary part) is heated, and the tube wall at the end is welded to discharge. Space 2 is airtight. This completes PDP51.
  • the vent pipe with a glass ring has a phosphate-based glass ring force, and the side face of the ring is joined along at least part of the inner wall surface of the pipe section of the vent pipe. It is arranged inside.
  • that the glass ring is joined to the inner wall surface of the vent pipe means a state in which the glass ring is joined to the inner wall surface of the pipe section of the vent pipe, and the glass ring is joined to the flange section. The state is handled as a state where a glass ring is bonded to the inner wall surface of the ventilation pipe.
  • a vent pipe with a glass ring is obtained by heating and melting a phosphoric acid-based glass ring into, for example, a pipe of the vent pipe so that a through-hole of the ring remains. It is preferable that the bonding strength between the inner wall surface of the vent pipe and the ring is increased by fitting it into the pipe of the vent pipe through an adhesive material. However, the vent pipe force is not limited unless the ring slides easily. The ring may be simply fitted into the trachea. [0080] From the viewpoint of attaching the vent pipe more firmly on the panel, it is possible to use a vent pipe with a glass ring in which the end face of the phosphate glass ring protrudes outward from the end face of the vent pipe. preferable.
  • the phosphate glass ring 15 force pipe 12 has an end face 55 so that the entire circumference of the end face of the vent pipe is not hindered from being arranged in contact with the panel. Is preferably in a state of protruding outward.
  • the glass ring and the vent pipe are generally arranged so that the gravity with respect to the glass ring is applied to the narrow pipe portion of the vent pipe. For this reason, if a glass tube with a glass ring in which the end face of the ring protrudes outward from the end face of the vent pipe, the glass ring in the molten state is more reliably attached to the panel during the above installation work. Can be made.
  • Example 1 uses a phosphate glass ring 15 having a frustoconical outer shape shown in FIG. 4A and a flare portion-attached tube 12 having an inner wall-shaped enlarged diameter portion 53 corresponding to the outer shape of the glass ring 15.
  • the PDP was manufactured by attaching a tube on the panel lb so as to cover the hole 11 and incorporate the glass member 13 (see FIG. 4B).
  • the frit 'binder mixture is filled into a mold molding machine for forming a ring having a frustoconical outer shape, press-molded to form a molded body ring having a frustoconical outer shape, and then to 360 ° C.
  • the binder is removed by heating, and the molded ring is baked. As a result, a phosphate glass ring 15 having a frustoconical outer shape was produced.
  • the phosphoric acid-based glass ring was fitted into the tube of the flare portion-attached tube 12, and then fired at 420 ° C., thereby producing a vent tube 54 with a glass ring as shown in FIG. 4A.
  • a PDP shown in Fig. 1 was produced using a vent ring 54 with a glass ring.
  • the specific procedure for producing the PDP followed the PDP manufacturing method described above.
  • the firing temperature for forming the peripheral sealing wall 3 and the glass member 13 was set to 450 ° C.
  • the discharge space was filled with Xe-Ne gas as the discharge gas so that the pressure was 0.53 atm (400 Torr).
  • Example 2 was prepared using a mixture of 80% by mass of the above glass powder and 20% by mass of cordierite as a refractory lead-free filler and 90% by mass of camphor as a binder.
  • a phosphate glass ring 17 having a cylindrical outer shape and an inner wall-shaped enlarged-diameter portion 53 corresponding to the outer shape of the glass ring 17 were prepared.
  • the tube is attached to the panel lb so as to cover the hole 11 and incorporate the glass member 18 produced in the same manner as in Example 1 except that the tube with cylindrical portion 16 is used. (See Figure 5B).
  • Example 3 is a bell-shaped profile as shown in FIG. Example 1 except that a phosphoric acid-based glass ring 20 having a ring and a bell-attached tube 19 having a diameter-enlarged portion 53 having an inner wall surface corresponding to the outer shape of the glass ring 20 are used.
  • the PDP was manufactured by attaching a tube on the panel lb so as to cover the hole 11 and incorporate the glass member 21 (see FIG. 6B).
  • Comparative Example 1 instead of a glass ring having a shape built into a tube, a phosphate glass in which a stepped portion serving as a tray for the tube 12 with a flare portion is formed on the surface of the inner wall surface as shown in FIG. 7A.
  • the glass ring 22 produced in the same manner as in Example 1 except that the ring 22 was used was melted.
  • the glass member 23 formed by melting is in contact with the outer wall surface (outside of the tube) and the end surface of the tube and the panel lb, and the tube is mounted on the panel lb (see FIG. 7B).
  • Luminance is evaluated using a luminance meter (display color analyzer) for the PDP immediately after production and the PDP after being left in a high humidity environment of 70 ° C '95% RH for 100 days (after a long-term humidity resistance test). I went against it.
  • the results are shown in Table 1.
  • the lighting luminance is shown as a relative value when the luminance obtained from the PDP of Conventional Example 1 immediately after manufacture is 100%.
  • the PDPs of Examples 1 to 3 illuminate with the same initial value and the initial value of the conventional example even after the long-term humidity resistance test, and have excellent long-term moisture resistance. It was confirmed that it exerts sex. On the other hand, the PDP of Comparative Example 1 was inferior in long-term moisture resistance because no lighting was observed after the long-term moisture resistance test.
  • Comparative Example 1 the distance between the end face on the hole side of the tube and the panel was 85 ⁇ m. On the other hand, in Examples 1 to 3, the distance between the end surface on the hole side of the tube and the panel was less than 5 m, and the end surface of the tube and the panel were substantially in contact with each other.
  • Example 1 The PDPs of Example 1 and Comparative Example 1 were (1) 90 ° C '95% RH, (2) 107 ° C-95% RH, (3) 120 ° C '95% RH, ( 4) The sample was left in an environment of 121 ° C 100% RH and the number of days until the PDP stopped lighting was examined.
  • Comparative Example 1 (1) 32 days, (2) 67 days, (3) 28 days, Whereas (4) was 3 days, Example 1 was (1) more than 200 days, (2) more than 80 days, (3) more than 70 days, and (4) 37 days.
  • Comparative Example 1 the phosphate glass member involved in mounting the tube on the panel is exposed to the outside air, and the end surface of the tube is not sufficiently close to the panel. It is thought that the airtightness of the discharge space was lowered due to erosion by the moisture inside.
  • Examples 1 to 3 when the end surface of the tube is in contact with the panel, the contact of moisture in the outside air with the phosphate glass member involved in the mounting of the tube on the panel is inhibited, and the discharge space is hermetically sealed. Can be maintained for a long time.
  • the amount of lead which is a harmful chemical substance, can be reduced to reduce adverse effects on the natural environment, and its long-term moisture resistance can be improved.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Glass Compositions (AREA)
  • Manufacture Of Electron Tubes, Discharge Lamp Vessels, Lead-In Wires, And The Like (AREA)
  • Gas-Filled Discharge Tubes (AREA)
  • Vessels, Lead-In Wires, Accessory Apparatuses For Cathode-Ray Tubes (AREA)

Abstract

La présente invention concerne un procédé permettant de réduire la quantité de plomb utilisée dans un dispositif d’affichage et d’améliorer sa résistance à l’humidité. Un dispositif d’affichage (51) comprend un panneau (1b) muni d’un orifice (11), un anneau de verre (13) formé d’un verre de phosphate sans plomb, et un évent (12) recouvrant l’orifice. L’anneau de verre réunit la face interne de l’évent à la face externe du panneau. L’anneau de verre se trouve sur la face interne de l’évent et n’est donc pas attaqué par l’humidité que contient l’air extérieur.
PCT/JP2006/322473 2005-11-11 2006-11-10 Dispositif d’affichage, event a anneau de verre, anneau de verre de phosphate, et procede de production correspondant WO2007055323A1 (fr)

Priority Applications (3)

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US12/092,768 US20100006313A1 (en) 2005-11-11 2006-11-10 Display device, vent tube with glass ring, phosphate glass ring, and method of producing the same
JP2007544197A JP4124804B2 (ja) 2005-11-11 2006-11-10 ディスプレイデバイス、ガラスリング付き通気管、リン酸系ガラスリングの製造方法
US12/495,257 US7737619B2 (en) 2005-11-11 2009-06-30 Display device, vent tube with glass ring, phosphate glass ring, and method of producing the same

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JP2005-327505 2005-11-11
JP2005-327507 2005-11-11
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JP2005327507 2005-11-11

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US12/092,768 A-371-Of-International US20100006313A1 (en) 2005-11-11 2006-11-10 Display device, vent tube with glass ring, phosphate glass ring, and method of producing the same
US12/495,257 Continuation US7737619B2 (en) 2005-11-11 2009-06-30 Display device, vent tube with glass ring, phosphate glass ring, and method of producing the same

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JP2009084108A (ja) * 2007-09-28 2009-04-23 Sekisui Chem Co Ltd 非鉛系ガラス微粒子分散ペースト組成物

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WO2006064733A1 (fr) * 2004-12-16 2006-06-22 Matsushita Electric Industrial Co., Ltd. Panneau d’affichage a plasma, son procede de fabrication et element d’etancheite
KR101046236B1 (ko) * 2009-04-01 2011-07-04 (주) 센불 평판 디스플레이 패널의 실링 소자 및 이를 포함하는 실링 소자-배기관 어셈블리
KR101130296B1 (ko) * 2009-12-23 2012-03-22 삼성에스디아이 주식회사 플라즈마 디스플레이 패널 격벽 형성용 감광성 페이스트 조성물
JP2011187330A (ja) * 2010-03-09 2011-09-22 Hitachi Consumer Electronics Co Ltd プラズマディスプレイパネル及びプラズマディスプレイパネルの製造用チャンバー
KR20120139392A (ko) * 2011-06-17 2012-12-27 삼성디스플레이 주식회사 디스플레이 패널, 그 제조방법 및 이에 사용되는 프릿 조성물
FR2985631B1 (fr) * 2012-01-09 2014-03-14 Hikob Boitier pour dispositif electronique

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US7737619B2 (en) 2010-06-15
US20100006313A1 (en) 2010-01-14

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